AU665578B2 - Starch mixture, process for the production thereof and use thereof - Google Patents
Starch mixture, process for the production thereof and use thereof Download PDFInfo
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- AU665578B2 AU665578B2 AU26134/92A AU2613492A AU665578B2 AU 665578 B2 AU665578 B2 AU 665578B2 AU 26134/92 A AU26134/92 A AU 26134/92A AU 2613492 A AU2613492 A AU 2613492A AU 665578 B2 AU665578 B2 AU 665578B2
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- starch
- starch mixture
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- 239000000203 mixture Substances 0.000 title claims description 102
- 229920002472 Starch Polymers 0.000 title claims description 98
- 235000019698 starch Nutrition 0.000 title claims description 98
- 239000008107 starch Substances 0.000 title claims description 96
- 238000000034 method Methods 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title description 11
- 239000002253 acid Substances 0.000 claims description 19
- 238000002844 melting Methods 0.000 claims description 19
- 230000008018 melting Effects 0.000 claims description 19
- 229920000881 Modified starch Polymers 0.000 claims description 18
- 239000004368 Modified starch Substances 0.000 claims description 18
- 239000000654 additive Substances 0.000 claims description 18
- 235000019426 modified starch Nutrition 0.000 claims description 18
- 239000004952 Polyamide Substances 0.000 claims description 17
- 229920002647 polyamide Polymers 0.000 claims description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 16
- 239000004202 carbamide Substances 0.000 claims description 16
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 239000000155 melt Substances 0.000 claims description 15
- 239000003995 emulsifying agent Substances 0.000 claims description 13
- 239000004014 plasticizer Substances 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 10
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 10
- -1 polyethylene Polymers 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 8
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 8
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 7
- 239000000600 sorbitol Substances 0.000 claims description 7
- 229920000856 Amylose Polymers 0.000 claims description 6
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical group OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 6
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 6
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 6
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 6
- 238000006467 substitution reaction Methods 0.000 claims description 6
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 5
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- 238000001746 injection moulding Methods 0.000 claims description 5
- 150000003672 ureas Chemical class 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 4
- 235000011037 adipic acid Nutrition 0.000 claims description 4
- 229960002684 aminocaproic acid Drugs 0.000 claims description 4
- 238000000071 blow moulding Methods 0.000 claims description 4
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 4
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 235000019359 magnesium stearate Nutrition 0.000 claims description 4
- 239000008239 natural water Substances 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 4
- 238000003856 thermoforming Methods 0.000 claims description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 4
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 3
- QJGNSTCICFBACB-UHFFFAOYSA-N 2-octylpropanedioic acid Chemical compound CCCCCCCCC(C(O)=O)C(O)=O QJGNSTCICFBACB-UHFFFAOYSA-N 0.000 claims description 3
- 239000004953 Aliphatic polyamide Substances 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- 229920003231 aliphatic polyamide Polymers 0.000 claims description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000000975 dye Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 229930195725 Mannitol Natural products 0.000 claims description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 claims description 2
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 claims description 2
- 229920006017 homo-polyamide Polymers 0.000 claims description 2
- 239000001341 hydroxy propyl starch Substances 0.000 claims description 2
- 235000013828 hydroxypropyl starch Nutrition 0.000 claims description 2
- 239000000594 mannitol Substances 0.000 claims description 2
- 235000010355 mannitol Nutrition 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- 150000002894 organic compounds Chemical group 0.000 claims description 2
- 229920001748 polybutylene Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 239000001194 polyoxyethylene (40) stearate Substances 0.000 claims description 2
- 235000011185 polyoxyethylene (40) stearate Nutrition 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 239000004743 Polypropylene Substances 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims 1
- 229920001155 polypropylene Polymers 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229920002292 Nylon 6 Polymers 0.000 description 8
- 229920000299 Nylon 12 Polymers 0.000 description 7
- 239000008187 granular material Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 229920003620 Grilon® Polymers 0.000 description 6
- 229920001169 thermoplastic Polymers 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920002959 polymer blend Polymers 0.000 description 4
- 238000002156 mixing Methods 0.000 description 3
- 229920002261 Corn starch Polymers 0.000 description 2
- JPNZKPRONVOMLL-UHFFFAOYSA-N azane;octadecanoic acid Chemical class [NH4+].CCCCCCCCCCCCCCCCCC([O-])=O JPNZKPRONVOMLL-UHFFFAOYSA-N 0.000 description 2
- 239000008120 corn starch Substances 0.000 description 2
- 229940099112 cornstarch Drugs 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920012196 Polyoxymethylene Copolymer Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010104 thermoplastic forming Methods 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/04—Starch derivatives, e.g. crosslinked derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Description
AUSTRALIA
Patents Act 665578 COMPLETE SPECIFICATION
(ORIGINAL)
Class Int. Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published.
Priority Related Art: 0
C
0 0* 0**0 Name of Applicant: Ems-Inventa AG Actual Inventor(s): Friedrich Severin Buehler Hans-Joachim Schultze Eduard Schmid Address for Service: PHILLIPS ORMONDE FITZPATRICK Patent and Trade Mark Attorneys 367 Collins Street Melbourne 3000 AUSTRALIA Invention Title: STARCH MIXTURE, PROCESS FOR THE PRODUCTION THEREOF AND USE THEREOF Our Ref 305476 POF Code: 3856/3856 The following statement is a full description of this invention, including the best method of performing it known to applicant(s): 6006 STARCH MIXTURES, PROCESS FOR THE PRODUCTION THEREOF AND USES THEREOF The invention relates to starch mixtures and uses thereof. In particular, the invention relates to a highly transparent, single-phased, biologically degradable starch mixture consisting of selected biologically degradable polyamide and a starch moulding composition which preferably contains emulsifier and/or urea and/or derivatives thereof in addition to chemically modified starch and plasticiser. The invention also relates to a process for producing this highly transparent starch mixture. In particular, the invention relates to the use of this starch mixture for producing thermoplastically shaped parts, in particular films, by 15 injection moulding, extrusion, co-extrusion, blow moulding, injection stamping and thermo forming.
As starch is a vegetable carbohydrate, there have been attempts to use it as a so-called "natural plastics material" in a wide variety of spheres, employing known plastics 20 processing methods. However, owing to their granular
S.
structure, native starches first have to be destructured before they are thermoplastically processible.
In order to impart the good properties known and desired of plastics materials to an opaque basic starch moulding composition of this type, it is necessary further to process it. It often loses its biological degradability in the process of doing this.
EP 0 344 118 A2 relates to a polymer blend material consisting of a melt of at least one water-containing destructured hydrophilic polymer and at least one synthetic, substantially water-insoluble thermoplastic polymer. An improvement in the dimensional stability by the addition of the water-insoluble polymer is demonstrated by examples of blends based on gelatins as well as cellulose derivatives and polyethylene, polystyrene, polyvinylether, polyoxymethylene and ethylene acrylic acid copolymers. However, the reference given there to possible biological degradability, namely the loss of this additional stability after several days, is 39 -2considered as a disadvantage for the products shaped from the blends without actually stating anything about the biological degradability.
EP-OS 0 327 505 A2 describes a melt-mixed polymer blend material consisting of destructured but chemically unmodified starch and at least one water-insoluble synthetic thermoplastic polymer.
Similarly, polymer blend compositions consisting of destructured starch, which is also chemically unmodified, and a functionalised polymer are known from the publicly distributed printed copies of the application papers, EP 0 409 789 A2, EP 0 409 788 A2, EP 0 409 783 A2, EP 0 409 782 A2, EP 0 409 781 Al, EP 0 408 503 A2, EP 0 408 502 A2, EP 0 408 501 A2, EP 0 407 350 A2, EP 0 404 728 A2, EP 0 404 723 A2 and EP 0 404 727 A2.
These ccmpositions may each additionally contain a further water-insoluble thermoplastic polymer. In this case, the functioralised polymer acts as a compatibilizer between the chemically unmodified starch and the additional third 20 thermoplastic polymer.
German Patent Application DE 4 119 915.4 describes starch polymer mixtures consisting of a starch moulding composition and selected linear polymers. Their specific disadvantage as well as that of all starch materials protected in the above-mentioned specifications is their typical yellow tinge as well as their non-transparency. However, opaque material can be used only to a limited extent, in particular in the packaging sphere, as the usual transparency of plastics materials is required here.
3- It has surprisingly been found -that a higl ly transparent, single-phased and biologically degrada starch mixture may be produced from a starch mou- ng composition, which contains chemically modifie arch, and a selected biologically degradable p mide, without addition of a polymeric compatibii r for thermoplastic processing.
The ly transparent single-phased, biologically de a le starch mixture according to the invention consists 39 -3- 3a According to an aspect of this invention there is provided a starch mixture which is highly transparent, single-phased and biologically degradable including the following components: ka) 10 to 99 parts by weight of a starch moulding composition consisting of; 96 to 56 parts by weight of at least one chemically modified starch, (ii) 4 to 40 parts by weight of at least one plasticiser, (iii) 0 to 4 parts by weight of at least one additive, wherein the parts by weight of (ii) and (iii) add up to 100 parts by weight, and 90 to 1 parts by weight of at least one aliphatic polyamide, which is a homopolyamide or copolyamide of o-aminocaproic acid, o-aminoenanthic acid, co- aminocaprylic acid, o-aminopelargonic acid, co-aminocapric acid, coaminoundecylic acid, co-aminolauric acid and/or caprolactam, lactam-7, lactam-8, lactam-9, lactam-10, lactum-11, laurolactam and/or of methylene diamine, dimethylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine and oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decane-dicarboxylic acid, undecanedioic 20 acid, dodecanedioic acid.
Optionally the starch mixture may include 0 to 20 parts by weight of additives corresponding to the prior art.
The chemically modified starch to be used according to the invention .typically has a natural water content of 5 to 16% by wight, preferably 5 to 12% by 25 weight, particularly preferably 6 to 8% by weight. This generally results in a final water content in the highly transparent starch mixture of 2 to 8% by weight, preferably 2 to 5% by weight..
•0•o0 DG C:,\WNORDODEULANODELETE\2B134 DC composition consisting of 96 to 56 parts by weight of at least one che ically modified starch (ii) 4 to 40 parts by weight of at least one plas ciser (iii) 0 to 4 parts by weight of at least e additive, in particular selected from urea and/or ure derivatives and/or emulsifiers wherein the parts by weight o (ii) and (iii) add up to 100 parts by weight and 90 to 1 parts by weight of t least one selected polyamide, wherein the parts b/ weight of components and (b) add up to 100 parts by ight and optionally addj ionally 0 to 20 part by weight of additives corresponding to the prior art.
The oemically modified starch to be used according to the inv tion has a natural water content of 5 to 16% by weig preferably 5 to 12% by weight, particularly preferably 20 6to 8% by weight. This generally results in a final water **content in the highly transparent starch mixture of 2 to 8% by weight, preferably 2 to 5% by weight.
The preferably used starch moulding composition is produced by a special process which is described in German Patent Application DE 41 17 628.6, wherein chemically modified starch having a natural water content, at least one plasticiser and urea and/or urea derivatives as well as at least one emulsifier such as metal stearates, glycerol monostearate, polyoxyethylene(20)-sorbitane monolaurate, polyoxyethylene(20)-sorbitane monopalmitate, polyoxyethylene(100)-stearate or a mixture thereof are destructurized at sufficiently elevated temperatures and pressures in an extruder and are extruded as a melt.
This above-mentioned process for producing a homogeneous, thermoplastically processible melt from chemically modified starch comprises the following process steps: 39 -4a) introduction of a chemically modified starch into the intake region of an extruder and conveyance thereof, b) addition of a pre-homogenised liquid anhydrous plasticiser-emulsifier-additive mixture, mixing thereof with the starch with simultaneous conveyance of the starch-plasticiser-emulsifier-additive mixture, c) destructurization of the starch granules without addition of extraneous water and complete plasticisation of said mixture to a homogeneous, thermoplastically processible melt and the conveyance thereof, d) degasification of the melt and further conveyance thereof, e) extrusion of the melt through a die, said mixture or melt being exposed to sufficiently elevated temperatures in steps b) to a reduced pressure in step d) and an elevated pressure in step or the following process steps a) separate introduction of a chemically modified starch and a plasticiser into the intake region of an extruder, mixing and conveyance thereof, 20 b) addition of a pre-homogenised, liquid, anhydrous emulsifier-additive mixture, mixing thereof with the starch-plasticiser-mixture with simultaneous conveyance of the starch-plasticiser-emulsifier-additive mixture, c) destructurization of the starch granules without addition of extraneous water and complete plasticisation of said mixture to a homogeneous, thermoplastically processible melt and conveyance thereof, d) degasification of the melt and further conveyance thereof, e) extrusion of the melt through a die, wherein said mixture or melt is exposed to sufficiently elevated temperatures in steps b) to a reduced pressure in step d) and an elevated pressure in step e).
The chemically modified starch has been modified by reaction of its OH-groups with alkylene oxides or other ether-, ester-, urethane-, carbamate- and/or isocyanate-forming substances. Hydroxy-C 2 to C 6 -alkyl, acetyl or carbamate starches or mixtures thereof are preferred.
39 The degree of substitution of the chemically modified starch is0O.01 to 0.2 and the amylose content is 20 to 3)0% by weight, preferably 50 to 100% by weight, particularly preferably 65 to 100% by weight.
Typi;wlly -ke plasticiser is an organic compound containing at least 1 hydroxyl group, preferably polyol, particularly preferably sorbitol, mannitol, D-glucose, ethylene glycol, polyethylene glycol, propylene glycol or mixtures thereof. It is used in quantities of 4 to 40 parts by weight, preferably 9 to 40 parts by weight, particularly preferably 10 to 30 parts by weight.
The additive, of which there is at least one, is added in quantities of 0 to 4 parts by weight. Urea and/or urea 1 derivatives and/or emulsifiers are preferred.
15 The urea and/or the urea derivatives, if used at all, are used in quantitites of 0.1 to 2 parts by weight, preferably 0.1 to 1 part by weight, particularly preferably 1 part by weight. The emulsifier has a hydrophilic-lipophilic balance tVP'Cq I .i 20 value of 0 to 20, preferably 10 to 20 and, if used at all, is used in quantitites of 0.1 to 1 parts by weight, particularly preferably 0.2 parts by weight. Suitable emulsifiers include metal stearates, glycerol monostearates, Polyoxyethylene(20)-sorbitane monolaurate, Polyoxyethylene(20)-sorbitane monopalmitate, Polyoxyethylene(40)-stearate, and/or Polyoxyethylene(100)-stearate.
In a preferred embodiment, component consists of parts by weight of hydroxyethyl and/or hydroxypropyl starch having a degree of substitution of 0.06 and an amylose content of 50% by weight, 15 parts by weight of glycerol, 13.8 parts by weight of sorbitol, 1 part by weight of urea and 0.2 parts by weight of magnesium stearate.
Selected aliphatic polyamides having a melting or softening point of 50 to 160 C and a melt flow index (MFI) of 100 to 5000 Pa.s (at 160oC and 21.2 N) are suitable as component 39 I V -6- Hemopely amides and/or copolyamidcc of w aminocaprcn^!; acid, w-aminoenanthic acid, w-aminocaprylic acid, w-aminopelargonic acid, w-aminocapri acid, w-aminoundecylic acid, w-aminolauric acid and/or caprolactam, lactam-7, lactam-8, actam-9, lactam-11, laurolactam and/ of methylene diamine, dimethylene diamine, tri ethylene diamine, tetramethylene diamine, pentameth e diamine, hexamethylene diamine and oxalic acid, alonic acid, succinic acid, glutaric acid, adipic a pimelic acid, suberic acid, azelaic acid, sebacic a nonanedicarboxylic acid, decane-dicarboxylic acid, undocanedioic acid, 6d aneeanedie- acid.
Those of caprolactam, laurolactam, w-aminolauric acid, -aminocaproic acid, hexamethylene diamine and adipic acid 15 or mixtures thereof are preferred.
One or more of optical brighteners, stabilisers, antioxidants, flame proofing agents, dyes, fillers and processing aids may additionally be used as additives corresponding to the prior art in quantities of 0 to 20 parts 20 by weight as component In a preferred embodiment, the single-phased starch mixture according to the invention contains component in 50 to 95 parts by weight and component in 50 to 5 parts by weight, 70 to 95 parts by weight of component and 30 to parts by weight of component being particularly preferred.
The transparency of the starch mixture according to the invention is generally proof that it is single-phased.
The process for producing the highly transparent starch Cs cAreri^BA ^oo e 'ncK'a^' mixture according to the invention t-apepaswa the common fusion of components and in a ratio of 10/90 to 99/1 in an extruder or in an injection moulding machine at temperatures which are not higher than 10 0 C below the decomposition point of the starch and not lower than 50°C above the melting or softening point of the polyamide.
The starch mixture according to the invention can be further processed into highly transparent, thermoplastically shaped parts, a granulate preferably being produced in the first instance and then being used for the production of 39 -7shaped articles. These may be produced by injection moulding, blow moulding, extrusion, co-extrusion, injection stamping or thermo-forming. The production of mono- or co-extruded films which may be designed as flat or blown films is particularly preferred.
A specific embodiment of such films consists of 50 to parts by weight of the starch moulding composition (component and 50 to 5 parts by weight of selected polyamide (component Component may be added either during the production of the starch mixture or preferably to components and/or Advantages of the starch mixture according to the invention and shaped articles produced from it: 1. High transparency; 2. Very good, i.e. smooth, surfaces free from exudation marks; 3. Single phase without addition of a polymeric compatibilizer; 20 4. Biological degradability; 5. Good tensile strength at break and elongation at break; 6. Low moisture uptake from the air; therefore processibility to a granulate which is stable in storage; Simple processing into films and co-extruded films without a tendency to block formation and problems of tackiness 8. Good adhesion of the co-extruded film layers without addition of an adhesive; 9. Highly expandable films; Welding of the films possible using conventional heat sealing devices; 11. Anti-static behaviour of the shaped articles; 12. Shaped articles may be printed with water-soluble dyes.
During the production of co-extruded films from the highly transparent starch mixture according to the invention and further polymers, these further polymers must have a melting or softening point of 50 to 160 0 C. Polyamides, polyesters and/or polyolefins are suitable for this purpose.
Polyolefins selected from the group comprising polyethylene, 39 -8polypropylene, polybutylene and derivatives thereof are preferred. Polyethylene and/or derivatives thereof is particularly preferred.
In a specific embodiment, the highly transparent starch mixture forms the middle layer and the further polymer(s) the internal and external layer of the co-extruded film. The starch mixture layer may also appear several times in the case of more than three film layers. In further embodiments of the co-extruded film, the highly transparent starch mixture may also form the internal and/or external layer.
All Eilms or sheets may be produced in a thickness of to 500 1 m, preferably 50 to 100 pm.
The films or sheets are suitable, for example, for the production of carrier bags, sacks, refuse bags, agricultural 15 films, diaper covering films and for biologically degradable films and sheets of any type.
Furthermore, all films may be subjected to a thermoplastic forming process such as deep drawing.
The following examples illustrate the invention without 20 restricting it.
I. Production rf the starch moulding composition (component Example la) A starch moulding composition was produced from 70 parts by weight of hydroxypropyl cornstarch having a degree of substitution of 0.06 and an amylose content of 50% by weight as wel -s 15 parts by weight of glycerol, 12.8 parts by weight of sorbitol, 2 parts by weight of urea and 0.2 parts by weight of magnesium stearate by the process described hereinafter and was subsequently granulated.
Extruder data: a) Heating zones: Room temperature 1300C 130 0
C
10 0 0° 1000C 150 0
C
b) Pressure: zone (30-40 bar) 3 x 106 to 4 x 106 P 39 -9c) Torque: d) Vacuum: bar) -4 x 104 Pa.
parts by weight of hydroxypropyl cornstarch having a degree of substitution of 0.06 and an amylose content of by weight and 12.8% by weight of sorbitol were introduced separately at point 7 in Figure 1 into the intake region (heating zone 1) of a co-rotating intermeshing twin screw extruder, screw geometry according to Figure 1 and a screw length to diameter ratio of 41, and were simultaneously mixed and conveyed in the extruder. 0.2% by weight of magnesium stearate were dissolved with 2% by weight of urea at 60oC in by weight of glycerol. This pre-homogenised .plasticiser-emulsifier-additive mixture was introduced into the extruder (heating zone 2) at point 8 in Figure 1 then 15 simultaneously mixed and conveyed on in the extruder. After destructurization of the starch granules and complete plasticisation of the starch mixture in the kneading chamber 11 (heating zones 2 and 3) to form a homogeneous melt, the starch melt was degasified by application of a vacuum at point 20 9 in Figure 1 (heating zone After passing through heating zone the homogeneous, thermoplastically processible starch melt was extruded through a die in heating zone as a strand having low strand expansion (die: 3 mm, strand: 4 mm), cooled and granulated.
Example lb) As Example la), but with a urea content of 1 par. by 0* S. weight and a sorbitol content of 13.8 parts by weight.
II. Production of the biologically degradable, single-phased highly transparent starch mixture Comparison Examples 2 to 12 and Examples 13 to 24 according to the invention The starch granulate from Example la) or Ib) was mixed with the granulate of the selected polyamide (component and was introduced into the metering zone of a twin screw extruder ZSK-30 (made by Werner Pfleiderer) with 6 heating zones. Speed and throughput were 100 rpm and 8 to 10 kg/h respectively.
The material properties of the resultant starch mixtures 39 may be inferred from Taiile 2.
The melt viscosities of the polya- s (component were determined at 160 0 C and 21.2 N in accordance with DIN 53 735. The melt viscosities of the starch mixtures were measured at 160°C and 236.4 N by a modified melt flow index method. The water content was determined by the Karl-Fischer method in accordance with DIN 53 714 and the melting point by differential calorimetry in the dry state at a heating rate of 0 C/min in a Du Pont Thermal Analyzer device, type 1091B.
The mechanical properties were determined in the dry state by means of injection moulded test rods according to DIN 53 457 (elongation modulus) and DIN 53 455 (tensile strength at break and elongation at break).
en.
The resistance to moisture was determined in cold water 15 by measuring the swelling. For this purpose, pieces of film measuring 100 cm 2 were left in cold water for one hour and their water uptake was then determined by weight measurement.
The dissolution of the starch mixtures in hot water is a condition for their biological degradability.
20 The following commercial products were used in the Examples and Comparison Examples: Grilon CF 62 BSE is a copolyamide based on the monomers of polyamide 6 and polyamide 6.9 made by EMS-CHEMIE and having a melting point of about 136 C Grilon CR 9 is a copolyamide based on the monomers of polyamide 6 and polyamide 12 made by EMS-CHEMIE and having a melting point of about 200 C Grilon CA 6E is a copolyamide based on the monome:-s of polyamide 6 and polyamide 12 made by EMS-CFEMIE and having a melting point of about 130°C Grilamide ELY 60 is a copolyamide made by EMS-CHEMIE, based on lactam-12, polyether diamine and dimerised fatty acid and having a melting point of about 1600C Griltex 1 is a copolyamide made by EMS-CHEMIE, based on tae monomers of polyamide 6, polyamide 12 and polyan'ide 6.6 and having a melting point of about 110°C and a melt viscosity (DIN 53 735) of about 600 Pa.s (21.2 N/160 0
C)
Griltex 2 is a copolyamide made by EMS-CHEMIE, based on 39 -ilthe monomers of polyamide 6, polyamide 12 and polyamide 6.6 and having a melting point of about 125°C and a melt viscosity (DIN 53 735) of about 400 Pa.s (21.2 N/160 0
C)
Griltex 3 is a copolyamide made by EMS-CHEMIE, based on the monomers of polyamide 6, polyamide 12 and polyamide 6.6 and having a melting point of about 110 C and a melt viscosity (DIN 53 735) of about 500 Pa.s (21.1 N/160 0
C)
Griltex 4 is a copolyamide made by EMS-CHEMIE, based on the monomers of polyamide 6, polyamide 12 and polyamide 6.6 and having a melting point of about 1100° and a melt viscosity (DIN 53 735) of about 100 Pa.s (21.2 N/160oC) Griltex 5 is a copolyamide made by EMS-CHEMIE, based on g the monomers of polyamide 6, polyamide 12, polyamide 6.6, polyamide 6.9 and polyamide 11 and having a melting point of 15 about 80 C and a melt viscosity (DIN 53 735) of about 150 Pa.s (21.2 N/160 0
C)
*i o too* too:
S
39 -12-
S
S.
p
S
S
a 0* Se S. S I is: 5 St C S s 0t e ses S S S S 55555
'I
TAble 1: Production parameters for the highly transparent starch mixtures according to the invention and comparison examples Polyamide 1 Content TypeExample Melting Melt 2 (Parts Starch Type Point Viscosity by Type TI T2 T3 T5 Tb IT3m oC) (Pa.s) weight Exaple (C 2a 2* Grion CT 62 BS 136 3100 50 la 0 140 145 145 145 150 167 3 Grilon CT 62 BSE 136 3100 460 la 0 140 145 11 145 5 150 163 4* Crilon CT 62 BS 136 3100 30 la 0 140 145 145 145 150 161 Crilon CF 62 BS 136 3100 20 la 0 140 145 145 145 150 157 64 Grilon CF 62 BSE 136 3100 10 Ila 0 140 145 145 145 150 165 7 Grilon CR 9 200 SO la 0 210 1230 230 230 240 235 8* Crilon CA 6E 130 3600 50 la 0 140 140 110 140 150 165 9* Crilamid ELY 60 160 50 Ia 0 150 170 150 150 170 179 Grilamid ELY 60 160 30 I 0 150 170 150 150 170 180 11 Grilamid ELY 60 160 10 Ila 0 150 170 150 150 170 178 12* Grilamid ELY 60 160 5 la 0 150 170 150 ISO 170 179 13 -Griltex 1 110 600 50 1l 0 150 1150 130 130 150 j 151 1 Griltex 1 110 600 40 lb 0 150 150 130 110 150 145 Griltex 1 110 600 30 lb 0 150 150 130 130 150 147 16 Gri3cex 1 110 600 20 lb 0 150 150 130 130 150 149 17 Griitex 1 110 600 50 lb 0 150 150 130 130 150 147 18 Griltex 1- 110 600 10 lb 0 150 150 130 130 150 153 19 Griltex 1 110 600 5 o 0 150 150 130 130 I 150 153 Griltex 2 125 400 150 lb 0 150 150 130 130 150 150 21 Griltex 2 1 125 400 20 lb 0 153 150 130 130 J 150 153 22 Griltex 3 110 500 50 lb 0 150 150 130 130 150 143 23 Griltex 4 ilo 100 50 ib 0 150 150 130 130 150 1 43 24 Griltex 5 5 50 150 50 lb 0 120 100 ;o00 100 130 J125 Comparison examples 1 Melting point according to DSC 2 Melt viscosity at 1600C and 21.2 3 Tm Melt temperature N according to DIN 53 735 Table 2: Material properties of highly transp&refi starctfpixtet.,accordig ,te, nve iiion and comparison examples prpr.. hl t B B B *B B* B B B B B B *B B B i I 3 1 6 Water Melting Melt Modulus Tensile Elongation Cold Hot water Trans- Example. of strength at break water dlssolutn. parency Colour by Point Viscosity Elast cit rat break swelling weight) (OC) (Pa.s) (N/mm (N/mm 2 2a 11.6 259 78 10.5 434 max. 10 Yes No 2* 4.4 107 1867 254 21.1 404 max. 1o Yes No 3* 2.2 111 4508., 499 17.5 221 max. Yes No 4* 1.8 115 6500 1038 26.6 4 max. 10 Yes No 1.6 113 8000 1393 30.4 3 max. 10 Yes No 6* Dissolutn. Yes No 7* I I No 7* No 8& No 4 13 5.5 143 215 117 14.6 434 max. io Yes Good 14 7.65 145 255 71 13.0 520 miax. 10 -Yes Godd 7.57 147 275 110 9.6 355 max. 1o Yes Very goo 16 8.11 149 271 89 6.4 220 Io 20 Yes Very goo 17 5J59: 147 263 max. 10 Yes Good 18 4.60 165 2840 190 9.3 64 Dissolutn. Yes Very goo 19 4.43 163 3575 160 8.2 65 Dissolutn. Yes Good 7.60 146 265 75 14.0 510 max. 10 Yes Very goo 21 8.05 148 283 92 .7.5 210 Dissolutnm. Yes Good 22 max. 10 Yes Good 23 max. 10 Yes No 24 1 1 11 Yes .No Comparison examples I Final water content according to DIN 53 714 2 Melting point according to DSC 3 Melt viscosity at 160 0 C and 236.4 N 4 Elongation modulus'according to DIN 53 457 5,6 accordrig to DIN 53 455
Claims (32)
1. A starch mixture which is highly transparent, single-phased and biologically degradable including the following components: 10 to 99 parts by weight of a starch moulding composition consisting of; 96 to 56 parts by weight of at least one chemically modified starch, (ii) 4 to 40 parts by weight of at least one plasticiser, (iii) 0 to 4 parts by weight of at least one additive, wherein the parts by weight of (ii) and (iii) add up to 100 parts by weight, and 90 to 1 parts by weight of at least one aliphatic polyamide, which is a homopolyamide or copolyamide of o-aminocaproic acid, o-aminoenanthic acid, o- aminocaprylic acid, o-aminopelargonic acid, o-aminocapric acid, o- aminoundecylic acid, o-aminolauric acid and/or caprolactam, lactam-7, lactam-8, lactam-9, lactam-10, lactum-11, laurolactam and/or of methylene diamine, dimethylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine and oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decane-dicarboxylic acid, undecanedioic 20 acid, dodecanedioic acid.
2. A starch mixture according to Claim 1, including 0 to 20 parts by weight of additive corresponding to the prior art.
3. A starch mixture according to Claim 1 or Claim 2, including 50 to parts by weight of component and 50 to 5 parts by weight of component 25
4. A starch mixture according to any one of Claims 1 to 3, wherein the chemically modified starch has a natural water content of 5 to 16% by weight. o.i
5. A starch mixture according to any one of Claims 1 to 4, wherein the chemically modified starch has an amylose content of 20 to 100% by weight.
6. A starch mixture according to any one of Claims 1 to 5, wherein the chemically modified starch is modified by reaction of its OH-groups with alkylene oxides or other ether-, ester-, urethane-, carbamate- and/or isocyanate- forming f4. substances. DG C:\WINWORDDEULAH4NODELLTE26134.DOC -16-
7. A starch mixture according to any one of Claims 1 to 6, wherein the chemically modified starch is a hydroxy-C 2 to C 6 -alkyl, acetyl, or carbamate starch or mixtures thereof.
8. A starch mixture according to any one of Claims 1 to 7, wherein the chemically modified starch has a degree of substitution of 0.01 to 0.2.
9. A starch mixture according to any one of Claims 1 to 8, wherein component contains 9 to 40 parts by weight of said plasticiser.
A starch mixture according to Claim 9, wherein component (a) contains 10 to 30 parts by weight of said plasticiser.
11. A starch mixture according to any one of Claims 1 to 10, wherein the plasticiser is an organic compound containing at least ,ne hydroxyl group.
12. A starch mixture according to Claim 11, wherein the plasticiser is selected from sorbitol, mannitol, D-glucose, glycerol, ethylene glycol, polethylene glycol, propylene glycol, and mixtures thereof.
13. A starch mixture according to any one of Claims 1 to 12, wherein the additive of component (iii) is selected from the group consisting of urea, urea derivatives and emulsifiers.
14. A starch mixture according to Claim 13, wherein component (iii) 2 comprises 0.1 to 2 parts by weight of urea and/or urea derivative'- and/or 0.1 to 2 parts by weight of at least one emulsifier.
A starch mixture according to Claim 13, wherein the additive of component (iii) comprises an emulsifier, the emulsifier being present in quantities of 0.1 to 1 parts by weight.
16. A starch mixture according to Claim 15, wherein the emulsifier is a 25 compound having a hydrophilic-lipophilic balance value of 0 to
17. A starch mixture according to Claim 15 or Claim 16, wherein the emulsifier is a compound selected from metal stearate, glycerol monostearate, polyoxyethlene(20)-sorbitane monolaurate, monopalmitate, polyoxyethylene(40)-stearate, polyoxyethylene(100)-stearate or mixtures thereof.
18. A starch mixture according to Claim 13, wherein the urea and/or urea derivative is present in quantities of 0.1 to 1% parts by weight. DG C:\vWNWORDDEULWEODELETB134.DC -17-
19. A starch mixture according to any one of Claims 1 to 18, wherein component consists of 70 parts by weight of hydroxyethyl and/or hydroxypropyl starch having a degree of substitution of 0.06 and an amylose content of 50% by weight, 15 parts by weight of glycerol, 13.8 parts by weight of sorbitol, 1 part by weight of urea and 0.2 parts by weight of magnesium stearate.
A starch mixture according to any one of Claims 1 to 19, wherein the polyamide is a caprolactam, laurolactam, o-aminolauric acid, c-aminocaproic acid, hexamethylene diamine and adipic acid or a mixture thereof.
21. A starch mixture according to Claim 2, wherein the additives corresponding to the prior art are selected from the group of optical brighteners and/or stabilizers and/or antioxidants and/or dyes and/or fillers and/or flame- proofing agents and/or processing aids.
22. A process for producing a starch mixture according to any one of Claims 1 to 21, wherein the components and are premixed in a ratio of 10:90 to 99:1 and are homogenously mixed in the melt at temperatures which are not higher than 10 0 C below the decomposition point of the starch and not lower than 50 OC above the melting point of the selected polyamide and are extruded or co-extruded.
23. Use of a starch mixture according to any one of Claims 1 to 22 for producing thermoplastically shaped parts by injection moulding, extrusion, co- extrusion, blow moulding, thermo forming or injection stamping.
24. Use of a starch mixture according to Claim 23 for producing thermoplastically shaped parts in the form of mono- or co-extruded films having a thickness of 20 to 500p.m.
25 25. Use of a starch mixture according to Claim 24 for producing monofilms consisting of 50 to 95 parts by weight of component and 50 to parts by weight of component
26. Use of a starch mixture according to Claim 25 for producing co- extruded films which consist of layers of the starch mixture and layers of at least one further selected polymer having a melting or softening point of 50 to 160 0 C. DG C:\WINWORR DELILAHNODELETE26134.DOC -18-
27. Use of a starch mixture according to Claim 26 for producing co- extruded films, the further polymer being selected from polyamide, polyester or polyolefin, or mixtures thereof.
28. Use of a starch mixture according to Claim 27 for producing co- extruded films, the polyolefin being selected from one or more of polyethylene, polypropylene, polybutylene and derivatives thereof.
29. Use of a starch mixture according to Claim 26 or Claim 27 for producing co-extruded films, wherein the starch mixture forms the middle layer and the further polymer(s) the internal and external layer.
30. Use of a starch mixture according to Claim 26 or Claim 27 for producing co-extruded films, wherein the starch mixture forms the internal and/or the internal layer.
31. A starch mixture substantially as herein described with reference to any one of the examples.
32. A process for producing a starch mixture substantially as herein described with reference to any one of the examples. DATED: 31 October, 1995 PHILLIPS ORMONDE FITZPATRICK i 20 Attorneys for: EMS-INVENA ib DG C;\WINWO.RDDEULLAHNODELETE26134.DOC ABSTRACT The invention relates to a highly transparent, singLe-phased and biologically degradable starch mixture consisting of 90 to 1 parts by weight of at least one selected polyamide and 10 to 99 parts by weight of starch moulding composition consisting of 96 to 56 parts by weight of at least one chemically modified starch and 4 to 40 parts by weight of at least one plasticiser and preferably up to 4 parts by weight of at least one additive selected from the group comprising urea, urea derivatives and emulsifier. In addition, the starch mixture may optionally contain up to 20 parts by :6 weight of additives corresponding to the prior art. The a 15 invention also relates to a process for producing the highly transparent starch mixture and, in particular, to the use of the starch mixture produced in this way in thermoplastically S shaped parts, in particular films, by injection moulding, extrusion, co-extrusion, blow moulding, injection stamping or thermo forming. a 000' *OO* *4 S 39
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4133335 | 1991-10-08 | ||
| DE4133335A DE4133335C2 (en) | 1991-10-08 | 1991-10-08 | Starch mixture, process for its preparation and use thereof |
Publications (2)
| Publication Number | Publication Date |
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| AU2613492A AU2613492A (en) | 1993-04-22 |
| AU665578B2 true AU665578B2 (en) | 1996-01-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU26134/92A Expired - Fee Related AU665578B2 (en) | 1991-10-08 | 1992-10-02 | Starch mixture, process for the production thereof and use thereof |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5436078A (en) |
| EP (1) | EP0536679A1 (en) |
| JP (1) | JPH05209091A (en) |
| AU (1) | AU665578B2 (en) |
| CA (1) | CA2080105A1 (en) |
| DE (1) | DE4133335C2 (en) |
| NZ (1) | NZ244658A (en) |
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| US8592641B2 (en) | 2006-12-15 | 2013-11-26 | Kimberly-Clark Worldwide, Inc. | Water-sensitive biodegradable film |
| FR2916203B1 (en) | 2007-05-14 | 2012-07-20 | Arkema | COEXTRUSION BINDERS BASED ON RENEWABLE / BIODEGRADABLE |
| US8329977B2 (en) * | 2007-08-22 | 2012-12-11 | Kimberly-Clark Worldwide, Inc. | Biodegradable water-sensitive films |
| FR2934272B1 (en) * | 2008-07-24 | 2013-08-16 | Roquette Freres | PROCESS FOR THE PREPARATION OF COMPOSITIONS BASED ON AMYLACEOUS MATERIAL AND SYNTHETIC POLYMER |
| US8907155B2 (en) | 2010-11-19 | 2014-12-09 | Kimberly-Clark Worldwide, Inc. | Biodegradable and flushable multi-layered film |
| US9718258B2 (en) | 2011-12-20 | 2017-08-01 | Kimberly-Clark Worldwide, Inc. | Multi-layered film containing a biopolymer |
| US9327438B2 (en) | 2011-12-20 | 2016-05-03 | Kimberly-Clark Worldwide, Inc. | Method for forming a thermoplastic composition that contains a plasticized starch polymer |
| KR20140111300A (en) | 2011-12-22 | 2014-09-18 | 플랜틱 테크놀로지스 리미티드 | Multilayer films |
| GB201217207D0 (en) * | 2012-09-26 | 2012-11-07 | Biome Bioplastics Ltd | Bio-resins |
| BE1021805B1 (en) * | 2013-11-05 | 2016-01-19 | Creachem Bvba | METHOD FOR INSULATING CARBOHYDRATE ALKYL CARBAMATES |
| FR3083544B1 (en) | 2018-07-06 | 2020-09-11 | Carbiolice | HIGH PLASTIC MATERIAL CONTAINING LACTIC ACID OLIGOMERS |
| FR3083543B1 (en) | 2018-07-06 | 2021-03-05 | Carbiolice | HIGH PLA PLASTIC MATERIAL INCLUDING A CITRATE ESTER |
| JP7246691B2 (en) * | 2018-12-14 | 2023-03-28 | 株式会社コバヤシ | resin composition |
| FR3094268B1 (en) | 2019-03-28 | 2021-03-19 | Carbiolice | MULTI-LAYER ENZYMED ARTICLE |
| FR3098519B1 (en) | 2019-07-10 | 2021-07-23 | Carbiolice | HIGH PLA PLASTIC MATERIAL INCLUDING PPGDGE |
| FR3106591B1 (en) | 2020-01-24 | 2022-08-05 | Carbiolice | USE OF AN ENZYME BLEND TO IMPROVE THE MECHANICAL PROPERTIES OF AN ARTICLE COMPRISING THE ENZYME BLEND AND A BIODEGRADABLE POLYMER |
| FR3139569A1 (en) | 2022-09-14 | 2024-03-15 | Carbiolice | SINGLE-LAYER ENZYMATED ARTICLE with water barrier properties |
| FR3139500B1 (en) | 2022-09-14 | 2024-09-27 | Carbiolice | ENZYMED MULTILAYER ARTICLE having water barrier properties |
| WO2025190969A1 (en) | 2024-03-12 | 2025-09-18 | Carbiolice | Enzyme-containing methanisable article |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU643144B2 (en) * | 1991-06-17 | 1993-11-04 | Ems-Inventa Ag | Starch/polymer mixture, process for the preparation thereof, and products obtainable therefrom |
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| US3598634A (en) * | 1968-11-05 | 1971-08-10 | Kraftco Corp | Coated packaging material |
| GB2214918B (en) * | 1988-02-03 | 1992-10-07 | Warner Lambert Co | Polymeric materials made from starch and at least one synthetic thermoplastic polymeric material |
| GB2218994B (en) * | 1988-05-26 | 1992-01-15 | Warner Lambert Co | New polymer composition |
| ATE126477T1 (en) * | 1989-06-01 | 1995-09-15 | Starch Australasia Limited | SHAPED OBJECTS DERIVED FROM STARCH. |
| IL94587A (en) * | 1989-06-19 | 1997-04-15 | Novon International | Polymer base blend compositions containing destructurized starch |
| IL94588A0 (en) * | 1989-06-22 | 1991-04-15 | Warner Lambert Co | Polymer base blend compositions containing destructurized starch |
| IL94589A0 (en) * | 1989-06-22 | 1991-04-15 | Warner Lambert Co | Polymer base blend compositions containing destructurized starch |
| IL94647A0 (en) * | 1989-07-06 | 1991-04-15 | Warner Lambert Co | Polymer base blend compositions containing destructurized starch |
| YU129090A (en) * | 1989-07-11 | 1992-12-21 | Warner-Lambert Company | PREPARATIONS OF POLYMER MIXTURES CONTAINING DESTRUCTURED STARCH |
| PT94594B (en) * | 1989-07-11 | 1997-02-28 | Warner Lambert Co | PROCESS FOR THE PREPARATION OF COMPOSITIONS OF POLYMERIC BASE MIXTURES CONTAINING DESERATED FROST |
| YU128990A (en) * | 1989-07-11 | 1993-05-28 | Warner-Lambert Co. | PREPARATIONS OF POLYMER MIXTURES CONTAINING DESTRUCTURED STARCH |
| JPH0725943B2 (en) * | 1989-07-18 | 1995-03-22 | ワーナー・ランバート・カンパニー | Polymer-based blend composition containing modified starch |
| FI102480B (en) * | 1989-07-18 | 1998-12-15 | Warner Lambert Co | Polymer-based blend compositions containing modified starch |
| PT94658B (en) * | 1989-07-18 | 1997-02-28 | Warner Lambert Co | PROCESS FOR THE PREPARATION OF POLYMERIC BASED COMPOSITIONS OF DESERATED FRUIT AND PRODUCTS THAT CONTAIN THEM |
| AU633462B2 (en) * | 1989-07-20 | 1993-01-28 | Novon International, Inc. | Polymer base blend compositions containing destructurized starch |
| JPH0725944B2 (en) * | 1989-07-20 | 1995-03-22 | ワーナー・ランバート・カンパニー | Polymer-based blend composition containing modified starch |
-
1991
- 1991-10-08 DE DE4133335A patent/DE4133335C2/en not_active Expired - Fee Related
-
1992
- 1992-10-02 AU AU26134/92A patent/AU665578B2/en not_active Expired - Fee Related
- 1992-10-06 EP EP92117004A patent/EP0536679A1/en not_active Withdrawn
- 1992-10-06 US US07/957,288 patent/US5436078A/en not_active Expired - Fee Related
- 1992-10-07 CA CA002080105A patent/CA2080105A1/en not_active Abandoned
- 1992-10-08 JP JP4269934A patent/JPH05209091A/en active Pending
- 1992-10-08 NZ NZ24465892A patent/NZ244658A/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU643144B2 (en) * | 1991-06-17 | 1993-11-04 | Ems-Inventa Ag | Starch/polymer mixture, process for the preparation thereof, and products obtainable therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| NZ244658A (en) | 1994-07-26 |
| JPH05209091A (en) | 1993-08-20 |
| CA2080105A1 (en) | 1993-04-09 |
| US5436078A (en) | 1995-07-25 |
| DE4133335A1 (en) | 1993-04-15 |
| EP0536679A1 (en) | 1993-04-14 |
| AU2613492A (en) | 1993-04-22 |
| DE4133335C2 (en) | 1995-11-02 |
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